JP2012246368A - Halogenated rhodamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye composition that exhibits high clarity and color-developability and excellent fastness such as heat resistance, moist heat resistance, water resistance and the like.SOLUTION: There are provided a compound represented by general formula (1), and an oil-based or water-based dye composition comprising the compound. In the formula, R-Rare each H, a halogen atom or an alkyl group; at least one of Rand Ris a halogen atom; R-Rare each H, an alkyl group or an aryl group; and Ris a carboxy group, a carboxylate group or an aminocarbonyl group.

Description

  The present invention relates to a novel rhodamine compound.

  Rhodamine dyes such as Rhodamine B, Rhodamine 3B, and Rhodamine 6G are widely used as red or violet dyes, and are used in a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, color filters, and dyes. Application has been made. In general, the characteristics required of a color material vary depending on the application, but it is particularly strongly required that the colored material is robust against light, heat, and the like.

  In general, rhodamine dyes are clear and have excellent color developability, but have the disadvantage of poor fastness such as light resistance, heat resistance, moist heat resistance, and water resistance. For this reason, there is a demand for dyes having the sharpness and color development of rhodamine dyes and having high fastness, but no rhodamine dyes having these properties have been found. Patent Document 1 describes a rhodamine dye composed of a cation moiety of a rhodamine compound and a chlorine ion or bromine ion. As a result of studies by the present inventors, the rhodamine dye described in Patent Document 1 is light-resistant. Fastness such as heat resistance, water resistance, and heat and humidity resistance was insufficient. Patent Document 2 describes a cationic dye having a tristrifluoromethanesulfonylmethide anion, but does not describe a rhodamine dye, and also provides fastness such as light resistance, heat resistance, moist heat resistance, and water resistance of the dye composition. There is no mention of sex.

Special table 2004-518766 JP-A-8-253705

  An object of this invention is to provide the novel rhodamine dye excellent in fastness, such as light resistance, heat resistance, heat-and-moisture resistance, and water resistance, and the dye composition using this dye.

  As a result of intensive studies to solve the above problems, the present inventors have found that rhodamine dyes having a specific structure dramatically improve fastness such as heat resistance as compared with the conventional ones. It came to complete.

（式（１）においてＲ_１〜Ｒ_４はそれぞれ独立に水素原子、ハロゲン原子またはアルキル基を表す。ただし、Ｒ_１およびＲ_２のうち少なくとも一つはハロゲン原子である。Ｒ_５〜Ｒ_８はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、Ｒ_９はカルボキシ基またはカルボン酸エステルまたはアミノカルボニル基を表す。）、
（２）一般式（１）においてＲ_１およびＲ_２が臭素原子である（１）に記載の化合物、
（３）（１）または（２）に記載の化合物と少なくとも１種類の油溶性有機溶媒を含有する油性染料組成物、
（４）（１）または（２）に記載の化合物及び水性媒体を含有する水性染料組成物、
に関する。 That is, the present invention
(1) Compound represented by general formula (1)

(In Formula (1), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group, provided that at least one of R ₁ and R ₂ is a halogen atom. R _{5 to} R ₈ are Each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ₉ represents a carboxy group, a carboxylic acid ester or an aminocarbonyl group).
(2) The compound according to (1), wherein R ₁ and R ₂ in the general formula (1) are bromine atoms,
(3) an oil-based dye composition containing the compound according to (1) or (2) and at least one oil-soluble organic solvent,
(4) An aqueous dye composition containing the compound according to (1) or (2) and an aqueous medium,
About.

  When the compound of the present invention forms an oily or aqueous dye composition to be processed into a dyed colored body, the compound exhibits characteristics superior in fastness to conventional products. That is, the compound of the present invention can be suitably used for dye-colored bodies, and can be applied to a wide range of uses such as color filters and inkjet inks.

  The compound of the present invention is represented by the formula (1).

In the general formula (1), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group. However, at least one of R ₁ and R ₂ is a halogen atom.

As a halogen atom in R < ₁ > -R < ₄ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

Examples of the alkyl group in R _{1 to} R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. These alkyl groups may have a substituent, for example, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group. Trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.

Both R ₁ and R ₂ are preferably halogen atoms, and particularly preferably bromine atoms.

R ₃ and R ₄ are preferably both alkyl groups, particularly preferably a methyl group or an ethyl group.

In the general formula (1), R _{5 to} R ₈ each independently represents a hydrogen atom, an alkyl group, or an aryl group.

Examples of the alkyl group in R _{5 to} R ₈ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. These alkyl groups may have a substituent, for example, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group. Trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.

Examples of the aryl group in R _{5 to} R ₈ include aromatic hydrocarbon residues such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, benzopyrenyl group; pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, An aromatic heterocyclic residue such as an isoquinolyl group, a pyrrolyl group, an indolenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group.

In R _{5 to} R ₈ , the aryl group may further have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and t-butyl. Group, alkyl group such as pentyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group and hexyloxy group; Hydroxyalkyl groups such as hydroxyethyl group and hydroxypropyl group; alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group and butoxyethyl group; hydroxyalkoxy groups such as 2-hydroxyethoxy group; 2-methoxyethoxy group , Alkoxyalkoxy groups such as 2-ethoxyethoxy group; 2-sulfoethyl , Carboxyethyl group, a cyanoethyl group, a sulfonic acid group, and the like.

In the general formula (1), R ₉ represents a carboxy group, a carboxylic acid ester, or an aminocarbonyl group.

Examples of the carboxylic acid ester in R ₉ include a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, an isobutyl ester group, a pentyl ester group, a cyclopentyl ester group, a hexyl ester group, and a cyclohexyl ester group. . These carboxylic acid ester groups may have a substituent, for example, hydroxyethyl ester group, hydroxypropyl ester group, hydroxybutyl ester group, 2-sulfoethyl ester group, carboxyethyl ester group, cyanoethyl ester group, methoxyethyl Examples thereof include an ester group, an ethoxyethyl ester group, a butoxyethyl ester group, a trifluoromethyl ester group, and a pentafluoroethyl ester group.

Examples of the aminocarbonyl group in R ₉ include a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group, a butylaminocarbonyl group, an isobutylaminocarbonyl group, a pentylaminocarbonyl group, a cyclopentylaminocarbonyl group, a hexylaminocarbonyl group, A cyclohexylaminocarbonyl group, and the like. These aminocarbonyl groups may have a substituent, for example, hydroxyethylaminocarbonyl group, hydroxypropylaminocarbonyl group, hydroxybutylaminocarbonyl group, 2-sulfoethylaminocarbonyl group, carboxyethylaminocarbonyl group, cyanoethylamino Examples include a carbonyl group, a methoxyethylaminocarbonyl group, an ethoxyethylaminocarbonyl group, a butoxyethylaminocarbonyl group, a trifluoromethylaminocarbonyl group, a pentafluoroethylaminocarbonyl group, a carbamoyl group, and the like.

  The compound of the present invention can be obtained by, for example, a known synthesis method described in Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (pages 373-375) published by Gihodo Co., Ltd. It can also be synthesized by synthesizing the rhodamine dye described in Document 1, and adding an alkali metal salt or acid of tristrifluoromethanesulfonylmethide to perform salt exchange.

  In the case of synthesizing the compound of the present invention by salt exchange, for example, a dye whose anion portion is a bromine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide (hereinafter referred to as “water”). And a water-soluble polar solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents may be used alone or in combination. The acid can be easily obtained by adding about 0.5 to 3 equivalents of acid, stirring at a predetermined temperature (for example, 0 to 100 ° C.), and collecting the precipitated crystals by filtration.

  Specific examples of the compound represented by the above formula (1) are shown in the following Table 1-1 to Table 1-3, but the present invention is not limited thereto.

表１−２

表１−３

表１−１〜表１−３において、Ｍｅはメチル基を、Ｅｔはエチル基を、それぞれ表す。 Table 1-1

Table 1-2

Table 1-3

In Table 1-1 to Table 1-3, Me represents a methyl group, and Et represents an ethyl group.

  The oily or aqueous dye composition of the present invention contains the compound of the present invention and an oil-soluble organic solvent in the case of an oily dye composition and an aqueous medium in the case of an aqueous dye. In the oily or aqueous dye composition of the present invention, the compound of the present invention is preferably contained in an amount of 0.2 to 40% by mass, and more preferably 0.5 to 20% by mass. In the oily or aqueous dye composition of the present invention, a colorant other than the formula (1) may be added as necessary for the purpose of adjusting the hue. Examples of colorants that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes, and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, and carbon black. And added in a dissolved or dispersed state in a solvent.

  The aqueous dye composition of the present invention can be prepared by dispersing the compound of the present invention in an aqueous medium. Examples of the aqueous medium include water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, benzyl alcohol, and the like; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monoethyl ether, triethylene glycol monobutyl ether Ether, dipropylene glycol monomethyl ether of glycol derivatives; ethanolamine, diethanolamine, triethanolamine, amines morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone, and the like.

  The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the compound of the present invention in at least one oil-soluble organic solvent. Examples of the oil-soluble organic solvent used include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; Butyl phenyl ether, benzyl ether, hex Ethers such as ether; Esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate; polar organics such as acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, 2-pyrrolidone A solvent etc. are mentioned, These solvents may be used independently and may mix and use 2 or more types.

  Dispersants used in oil dye compositions include sodium dodecylbenzenesulfonate, sodium laurate, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Known anionic surfactants such as ammonium salts of oxyethylene alkyl ether sulfates, ammonium of polyoxyethylene alkyl phenyl ether sulfates, polyoxyalkyl ether phosphate esters, vinyl naphthalene derivatives, fats of α, β-ethylenically unsaturated carboxylic acids Aromatic alcohol esters, etc., styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, maleic anhydride A block copolymer consisting of at least two monomers selected from inic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. A molecular dispersant etc. are mentioned, It is preferable to use between 10-100 mass% with respect to the pigment | dye compound which disperse | distributes 1 or more of these. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.

  As a method for dispersing the pigment into the fine particles, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like is used. Among them, a sand mill (bead mill) is generally used. For the grinding of pigments in sand mills (bead mills), it is necessary to use beads with small particle diameters and to process them under conditions that increase the grinding efficiency by increasing the filling rate of the beads. It is necessary to remove elementary particles by separation or the like.

  The dye composition of the present invention may contain a surface conditioner, preservative, antifungal agent, pH adjuster, etc. as other additives. As surface conditioning agents, polysiloxane or polydimethylsiloxane surfactants, and as antiseptic and mildewproofing agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide 1, 2-benzisothiazolin-3-one, amine salts of 1-benzisothiazolin-3-one, etc., and pH adjusters include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide And tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine.

  In addition, in the oily or aqueous dye composition of the present invention, a polyamide system, a polyurethane system, or a polyester system that is compatible with the medium in the composition within a necessary range for the purpose of improving the fixability of the pigment to the object to be colored. It is preferable to contain an epoxy or polyacrylic resin. Further, for the purpose of improving the fixability, a monomer, oligomer, polymerization initiator or the like having an ethylenically unsaturated group may be contained within a necessary range. The oily or aqueous dye composition of the present invention can be prepared by dissolving or dispersing and mixing the above components in a solvent.

  The compound of the present invention is used as an oil-based dye composition or an aqueous dye composition in various paints, water-based inks, oil-based inks, inkjet inks, and color filter coloring compositions. The oil-based dye composition and the aqueous dye composition are used for materials to be colored such as plain paper, coated paper, plastic film, and plastic substrate. Examples of a method for applying the dye composition of the present invention to a material to be colored include various printing methods such as offset printing, letterpress printing, flexographic printing, and ink jet printing, and coating methods using a spin coater, a roll coater, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In Examples, “part” means “part by mass” unless otherwise specified. In addition, evaluation of wet heat resistance, water resistance and the like was evaluated by measuring the chromaticity (L value, a value, b value) of the dyed colored body with a spectrophotometer “trade name UV-3150 manufactured by Shimadzu Corporation”.

Example 1 (Synthesis of Compound No. 1 in Table 1)
(Step 1-1)
A 1000 ml four-necked flask was charged with 6 parts of rhodamine 6G (manufactured by Tokyo Chemical Industry) and 395 parts of methanol, and stirred at room temperature for 10 minutes. To this, 4.2 parts of bromine was added dropwise and stirred at room temperature for 3 hours. After adding 2 parts of bromine and stirring for 1 hour, 1.3 parts of bromine was added and stirred for 30 minutes. The precipitated dye was collected by filtration, washed with methanol and water, and then dried to obtain 9.5 parts of a dye intermediate.
Maximum absorption wavelength (cyclohexanone): 550 nm. IR (KBr tablet method, cm ⁻¹ ): 3322, 3230, 2974, 2928, 1716, 1635, 1595, 1495, 1473, 1446, 1336, 1290, 1082.

(Step 1-2)
In a 3000 ml beaker, 5 parts of the dye intermediate obtained in Step 1-1, 790 parts of methanol, and 316 parts of acetone were charged and stirred at 30 ° C. for 30 minutes. A solution prepared by dissolving 3.4 parts of potassium salt of tristrifluoromethanesulfonylmethide (manufactured by Central Glass) in 4 parts of DMF was added dropwise thereto and stirred at room temperature for 3 hours. 1500 parts of water was added thereto, and the precipitated dye was collected by filtration, washed with 70% aqueous methanol, and dried to obtain 5.1 parts of a dye (compound of the present invention). By IR spectrum (cm ⁻¹ ), 1378 (S = O reverse stretching vibration), 1203 (S═O stretching vibration), 1127 (C—F stretching vibration) are observed, and the anion is converted to tristrifluoromethanesulfonylmethide anion. Confirmed that it was replaced.
Maximum absorption wavelength (cyclohexanone): 551 nm. IR (KBr tablet method, cm ⁻¹ ): 3400, 3356, 2983, 2938, 1711, 1637, 1595, 1498, 1475, 1448, 1378, 1330, 1286, 1203, 1127, 1085, 978.

Example 2 (Preparation of oil-based dye composition and dyed colored body)
In a 500 ml four-necked flask, 160 parts of propylene glycol monomethyl ether acetate, 6.6 parts of methacrylic acid, 30 parts of cyclohexyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate, 2 parts of α, α′-azobis (isobutyronitrile) Nitrogen gas was allowed to flow into the flask for 30 minutes while charging and stirring, and then the temperature was raised to 80 ° C. and stirred at 80 to 85 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature to obtain a colorless transparent and uniform liquid, that is, a copolymer solution. The polystyrene-reduced weight average molecular weight was 12000, and the acid value was 100.
Compound No. 1 obtained in Example 1 was added to 0.8 part of the copolymer obtained and 1 part of tetrafluoropropanol. 1 was dissolved to prepare an oil dye composition. The obtained oily dye composition was spin-coated on a glass substrate and dried at 200 ° C. for 20 minutes to prepare a dye-colored product.

In addition, the comparative example 1 in the following Table 3 uses a bromo salt compound of the following formula (100) and similarly produces a dye-colored product.

Heat Resistance Test The dyed colored product obtained by the above method was left in a constant temperature hot air dryer under the condition of 230 ° C. for 3 hours. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because there is little change of a hue, so that a color difference is small.
Color difference = [(L value before test−L value after test) ² + (a value before test−a value after test) ² + (b value before test−b value after test) ² ] ^1/2
The measured values and color difference of the colorimetry in the heat resistance test are shown in Tables 2 to 4 below.

Compound No. Table 2 below shows the colorimetric results of 1 dye-colored product.
(Table 2)
L value a value b value Before test 61.81 90.76 -48.30
After the test 62.33 88.28 -43.07
Difference before and after test -0.52 2.48 -5.23

The color measurement results of the dye-colored product of Comparative Example 1 are shown in Table 3 below.
(Table 3)
L value a value b value before test 90.02 16.51-6.68
After the test 98.47 0.41 0.83
Difference before and after test -8.45 16.10 -7.51

From Table 2 and Table 3 above, Compound No. Table 4 shows the results obtained by determining the color difference of the dyed colored bodies of No. 1 and Comparative Example 1.
(Table 4)
Color difference compound no. 1 5.8
Comparative Example 1 19.7

  As is apparent from the results in Table 4, the color difference before and after the test of the dye-colored product of Comparative Example 1 was as large as 19.7, whereas the dye-colored product of the present invention had an extremely large color difference of 5.8. A small value is shown, indicating that the heat resistance is extremely excellent.

Claims (4)

Compound represented by general formula (1)

(In Formula (1), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom or an alkyl group, provided that at least one of R ₁ and R ₂ is a halogen atom. R _{5 to} R ₈ are Each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ₉ represents a carboxy group, a carboxylic acid ester or an aminocarbonyl group). The compound according to claim 1, wherein R ₁ and R ₂ in the general formula (1) are bromine atoms. An oil-based dye composition comprising the compound according to claim 1 or 2 and at least one oil-soluble organic solvent. An aqueous dye composition comprising the compound according to claim 1 or 2 and an aqueous medium.